2-aryliminopyrrolidines and their production

ABSTRACT

2-Phenyliminopyrrolidines of the formula:   OR SALTS THEREOF, WHEREIN R1 is halogen, R2 is hydrogen, halogen, alkyl of 1 to 6 carbon atoms, difluoromethyl or trifluoromethyl, R3 is hydrogen or alkyl, preferably lower alkyl, N IS AN INTEGER FROM 1 TO 4, AND A, B and C each represent hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, or A and B, or B and C are linked to each other to form a ring, provided that at least one of A, B and C is alkyl or alkenyl, ARE USEFUL AS ACARICIDES.

United States Patent [191 Enders et al.

[ June 28, 1974 2-ARYLIMINOPYRROLIDINES AND THEIR PRODUCTION [75] Inventors: Edgar Enders, Cologne; Wilhelm Stendel, Wuppertal-Elberfeld; Jurgen-Dietrich Meier, Cologne; Marc Francque, Monheim, all of Germany [73] Assignee: Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany [22] Filed: Sept. 17, 1971 [2]] Appl. No.: 181,613

{30] Foreign Application Priority Data Sept. 19, 1970 Germany 2046413 [52] US. Cl.260/240 F, 260/3265 FL, 260/3265 L,

260/326.82, 260/326L85, 424/274 [5i] Int. Cl C07d 27/04 [58] Field of Search 260/326.85, 240 F {56] References Cited FOREIGN PATENTS OR APPLICATIONS 6,903,653 12/1969 South Africa OTHER PUBLICATIONS Enders et al., Chemical Abstracts, Vol. 73; l4673r (1970), Abs. of S. Afr., 6903653.

Primary ExaminerJoseph A. Narcavage [57] ABSTRACT 2-Phenyliminopyrrolidines of the formula:

are useful as acaricides.

59 Claims, N0 Drawings 2-ARYLIMINOPYRROLIDINES AND THEIR PRODUCTION The present invention relates to certain new 2-phenyl-iminopyrrolidines, to a process for their production, to acaricidal compositions and to their use as acaricides, especially in combating animal ectoparasites. i

More particularly, the compounds of the present invention are Z-phenyliminopyrrolidines of the formula:

R1 Gin-H,

1 R1 N= H:

and salts thereof, wherein R is halogen,

R is hydrogen, halogen, alkyl of l to 6 carbon atoms,

difluoromethyl or trifluoromethyl,

R is hydrogen or alkyl, preferably lower alkyl,

n is an integer from 1 to 4, and

A, B and C each represent hydrogen, alkyl of l to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, or A and B, or B and C are linked to each other .to form a ring, provided that at least one of A, B and C is alkyl or alkenyl,

These compounds exhibit strong acaricidal properties and are therefore useful for combating animal ectoparasites from the class of the acarids.

The compounds according to the present invention may be produced by condensing an arylamine of the formula:

(Rt)n (11) wherein R R and n are as above defined,

with a pyrrolidone of the formula:

(III) wherein R A, B and C are as above defined, in the presence of an agent which splits off water..The compounds of the present invention may, for example, be isolated in the form of their salts with hydrohalic acids or in the form of the free bases which may then be converted into suitable salts if desired. I

The condensation of 2,4-dtchloroaml1ne and N-isobutenyl-pyrrolidone can be represented by the following equation:

I POCls fl O \N/ /CH:

CH=C

Cl M i J JJH=C The arylamines defined by the formula (II) are known. R is preferably chlorine, bromine or fluorine. When R is halogen, it is preferably chlorine, bromine or fluorine; when it is alkyl, it is preferably methyl or ethyl.

Examples of arylamines of formula II) include: 2-, 3- and 4-chloroaniline, 2-, 3- 'and 4-bromoaniline, 2,4-

dichloroaniline, 3,4-dichloroaniline, 2,3- dichloroaniline, 2,5-dichloroaniline, 2,4,5- trichloroaniline, 2,4,6-trichloroaniline, 3,4,5-

trichloroaniline, 4-fluoro-3chloro-aniline, 4-fluoro-2- bromo-aniline, 2-chloro-4-bromo-aniline, 4-chloro-2- bromo-aniline, 2,4-dibromo-aniline, 4-bromo-2- methyl-aniline, 2,5-dichloro-4-bromo-aniline, 4,5dichloroQ-bromo-aniline, 2-fluoro-4-bromoaniline, 2,3,4-trichloro-aniline, 2,3,4,5-tetrachloroaniline, pentachloroaniline, 4-chloro-2-methylaniline, 2-chloro-4-methyl-aniline, 2,4-dichloro-5-methylaniline, 3,4-dichloro-6-methyl-aniline, 2-chloro-4- fluoro-aniline, 4-chloro-2-ethyl-aniline, 4-iodo-2- chloro-aniline, 4-bromo-2-ethylaniline, 4-bromo-2-isopropyl-aniline, 2-chloro-4-difluoromethyl-aniline, 2- chloro-4-trifluoromethyl-aniline, 4-chloro-2- difluoromethyl-aniline, 4-chloro-2-trifluoromethylaniline, 4-chloro-3- trifluoro-methyl-aniline and 3- chloro-4-trifluoromethyl-aniline.

The pyrrolidones of formula (III) are either known or can be produced according to known methods.

R is preferablyhydrogen; when it is alkyl, it is preferably alkyl of l to 4 carbon atoms.

When A and B are linked to each other to form a ring, it is preferred that a 6-membered ring is formed. The preferred alkyl and alkenyl groups are those having the appropriate number of carbon atoms to form a 6-membered ring.

Examples of pyrrolidones of formula (III) include: N-propenyl-pyrrolidone, N-isopropenyl-pyrrolidone, N-butenyl-pyrrolidone, N-isobutenyl-pyrrolidone, N-pentenyl-pyrrolidone, N-hexenyl-pyrrolidone, N- l,2-dimethyl-vinyl)-pyrrolidone, N-( 1,2,2-trimethylvinyl )-pyrrolidone, N-( l-ethyl-2-methyl-vinyl)- pyrrolidone, N-( lmethyl-Z-isopropyl-vinyl)- pyrrolidone, N-( 2-isopropyl-vinyl)-pyrrolidone, N-cyclopentenylpyrrolidone, N-cyclohexenylpyrrolidone, N-( 2,2-cyclo-tetramethylene-vinyl)- pyrrolidone, N-( 2,2-cyclopentylmethylene-Vinyl)- pyrrolidone, 4-( N-pyrrolidonyl-methylene cyclohexene and l(N-pyrrolidonyl)-butadiene.

N-isobutenyl-pyrrolidone can, for example, be produced be reacting pyrrolidone with isobutyraldehyde under the conditions of an azeotropic distillation, in the The reaction of the arylamine with the pyrrolidone derivative can be carried out in the presence of an inert diluent. Suitable diluents are organic solvents, for example aromatic hydrocarbons such as benzene, toluene and xylene, and chlorinated hydrocarbons such as chlorobenzene, O-dichlorobenzene, tetrachloromethane and tetrachloroethylene.

An inorganic acid halide, such as phosphorus oxychloride, phosphorus trichloride, thionyl chloride, phosphorus sulphochloride or phosgene is preferably used as the agent which splits off water.

The reaction temperatures can be varied over a wide range. In general, the reaction is carried out at to 120, preferably 60 to l0OC.

In carrying out the process, the two starting materials may be used in approximately equimolar amounts and an approximately equimolar amount of the agent which splits off water may be added. The reaction can be carried out in the presence of solvents, but preferably in the absence of any solvents. In general, all reactants are first brought together and the reaction mixture is then heated to higher temperatures, for example 60 -l00C. The reaction is complete when the aniline derivative employed can no longer be detected by diazotisation and coupling. The 2-phenylimino-pyrrolidines may be obtained as salts of hydrohalic acids, which are sparingly soluble in hydrocarbons or halogenated hydrocarbons. They can be isolated as such salts. Preferably, however, the salts produced are dissolved in water at room temperature, preferably a large amount of water, oily, insoluble by-products are removed, and the free bases are precipitated by the addition of aqueous sodium hydroxide solution. The basescan be filtered off as crystalline precipitates, or, if they possess low solidificationvpoints, can be extracted with organic solvents, dried and distilled. To prepare any desired salts, the free bases can be reacted with the corresponding acids, for example with inorganic acids such as sulphuric acid, hydrochloric acid or phosphoric acid, or with organic acids such as acetic acid, tartaric acid, citric acid, benzenesulphonic acid and naphthalene-1,5- disulphonic acid.

To prepare the compounds according to the invention, the arylamines of the formula (II) can also be reacted with pyrrolidine derivatives of the formula (VI) or (VII);

CH2 CH2 CHr-CH:

R3 R3 5:!) Hz 24 H: Y B \g/ B (1:8 =c

wherein IQ, A, B and C are as above defined,

Z is a reactive ester or ether group and Y 9 is the anion of an inorganic acid.

As examples, there may be mentioned N-isobutenyl- 2-thiopyrrolidone, N-isobutenyl-2-ethoxy-pyrrolinium tetrafluoborate, N-isobutenyl-Z-methylthiopyrrolinium methosulphate, N-isobutenyl-Z-chloropyrrolinium chloride or acetals such as N-isobutenyl-2,2-dimethoxy-pyrrolidine.

The compounds according to the invention can furthermore be obtained by splitting off alcohol or hydrogen halide from compounds of the formula (VIII) or (IX):

R R R n, A, B and C are as above defined,- R is alkyl of l to 6 carbon atoms, preferably methyl or ethyl, and Hal is chlorine or bromine. Finally, the compounds of the present invention can also be obtained by reacting pyrrolidine derivatives of the formula (X) with aldehydes or ketones of the formula (IX) while splitting off water, for example under the conditions of an azeotropic distillation in the presence of acid catalysts:

In the formulae (X) and (XI),

R R,, R-,, n, A, B and C are as above defined.

The 2-phenylimino-pyrrolidines as well as their salts display strong acaricidal properties, especially against acarids which as animal ectoparasites attack domesti-' cated animals such as cattle, sheep and rabbits. At the same time, the pryyolidine derivatives generally have only a low toxicity to warm-blooded animals. They are therefore well suited to combating animal ectoparasites of the class acarids. 1

The compounds of the present invention show a considerably better activity than similar 2-phenyliminopyrrolidines, such as have been disclosed in Belgian patent No. 734,934.

As economically important, harmful ectoparasites of the class of the acarids,-which play a major role especially in tropical and sub-tropical countries, there may be mentioned the Australian and the South American cattle tick, Boophilus microplus, and the South African cattle tick, Boophilus decoloratus, both from the family of the ixodidae. In the same way, representatives of the family of the sarcoptidae can also be combated, such as the rabbit ear mite, Psoroptes cuniculi.

Over the course of time, various ectoparasites, especially ticks, have become resistant to the phosphoric acid esters and carbamates hitherto used for combating them, so that in many areas the success in combating them has become increasingly doubtful. To ensure economical raising of animals in the areas where attack occurs, there is an urgent requirement for agents by means of which all stages of development, that is to say larvae, nymphs, metanymphs and adults, even of resistant strains, for example of the genus Boophilus, can be combated reliably. For example, in Australia the Ridgeland strain and the Biarra strain in Boophilus microplus are highly resistant to the phosphoric acid ester agents hitherto used [see also R. H. Wharton and W. J. Roulston, Annual Review of Entomology, volume 15 (1970), pages 381-404].

The compounds of the present invention are equally active both against the normally sensitive strains and against the resistant strains, for example of Boophilus.

On normal application to the host animal, they both have a direct lethal action on all forms existing as parasites on the animal, and a strong ovicidal action on the adult forms, so that the reproductive cycle of the ticks is interrupted both in the parasite phase on the animal and in the non-parasitic phase. The deposition of eggs is largely stopped and development and hatching inhibited.

The compounds of the present invention can be formulated into acaricidal compositions in the form of solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced according to techniques per se known, for example, by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifiying agents and/or dispersing agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic r aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions with boiling ranges of 120 400C. preferably 180 -300C, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide, pyrrolidone, N-methyl-pyrrolidone, hexamethylphosphoric acid amide or acetonitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, e. g., aerosol propellants, such as halogenated hydrocarbons, e.g., freon.

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.

Preferred examples of emulsifying agents include nonionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkyl-arylpolyglycol ethers, alkyl sulphonates, alkyl sulphates, quaternary ammonium salts with long chain alkyl moieties and aryl sulphonates; and preferred examples of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.

The acaricidal compositions of the present invention contain 0.1 to 95 percent by weight of active substance, preferably 0.5 to 90 percent by weight.

For application they may be diluted, for example with water. Depending on the form of use, the concentrations can be varied over a wide range and are generally from 10 to 50,000 ppm by weight, preferably 50 to 5,000 ppm.

Application may be effected in the usual manner, for example by spraying, watering or atomizing, or in a bath (dip).

Other additives of active substances, such as disinfectants, can be mixed with the formulations of the readyto-use solutions.

Aqueous solutions or emulsions of the compounds of the present invention possess good stability under practical conditions, so that they may remain active for up to three months or longer at a pH of 7 9.

The present invention also provides a method of combating acarid pests which comprises applying to the acarids or a habitat thereof a compound of the present invention per se or in the form of an acaricidal composition containing as the active ingredient a compound of the present invention in combination with a diluent or carrier.

The present invention also provides a method of protecting or freeing animals from ectoparasites which comprises applying externally to the animals a compound of the invention alone or in admixture with a diluent or carrier.

The following non-limitative examples more particularly illustrate the present invention.

EXAMPLE 1 3 N CH: (ilH=O 512 g of phosphorus oxychloride are added dropwise to a mixture of 500 g of N-isobutenyl-pyrrolidone and 543 g of 2,4-dichloroaniline at 15 20. Thereafter the mixture is stirred for a further hour at 20 and is then heated to until no further 2,4-dichloroaniline is detectable in a sample by diazotisation and coupling. Thereafter the batch is introduced into 30 litres of water at 20 25C, with stirring, and the mixture is stirred for one hour until only small amounts of oily material still remain undissolved. After adding active charcoal and'a filter aid,the acidic aqueous solution is clarified by filtration and adjusted to pH 8 8.5 and 20 30C by dropwise addition of 45 percent strength sodium hydroxide solution. Thereupon the reaction prodpension is stirred for a further of waterv After drying in vacuo, the yield is 830 g (87.5

percent of theory), melting point: 50 52C; after recrystallisation from petroleum ether, melting point: 545C. The purity, determined by gas chromatography, is 98 100 percent. The compound can be distilled and has a boiling point at a pressure of 0.2 mm

Hg of 155 158C.

The 2-arylimino-l-alkylvinyl-pyrrolidines of Exam ples 2-34 are analogously produced from the appropriate N-alkylvinyl-pyrrolidone and the arylamine.

Ex. No. Formulae of Examples 2-34 Physical constants 2... Boiling point 168 to 172 C./0.2

mm. Hg. 01- -N f Cl CH=C\ 3 Boiling point 162 to 166 C./O4 mm. Hg. Cl- N III CH3 1'130 CIIZC 4,. Boiling point 165 to 169 C./0.3 mm. Hg. CH3 N 1T1 CH3 C1 CH=C 5 Boiling point 171 to 176 C./O.3 N mm. Hg. Br H 111 CH: HaC CH=C CHa 6 Boiling point 172 to 176 C./0.3 mm. Hg. CH N III C113 Br CH=C 7- C2H5 Boiling point 172 I to 176 C./l.0

mm. Hg. Br- N:

CH=C

8 Boiling point; 162

to 166 O./0.3 mm. Hg F 'C- N 3 II I /CH3 1 Cl CH=C L (1 Boiling point 157 to 162 C./0.4 111111. 11g. N:

N on;

Ex. N0. Formulae of Examples 2-34- Pliysiuul constants 10. Cl Boiling point 158 10 162 C./U.3 mm. Hg.

N CH3 I H30 H:C\

11 C1 Boiling point 172 to 176 C./0.3 mm. Hg. 01- N l I\ I C H3 HaC CH=C 12- CH3 Boiling point 139 to 143 C./O.3

mm. Hg. N:

N on;

1 Cl C H C 13- CH: Boiling point 151 to 156 C./0.2 mm. Hg. N l 01 011:0

14. Boiling point 162 to 165 C./0.2 C1 N mm. Hg.

1 O1 CH=CH-C2H 15- Boiling point 157 to 163 C./O.3 CH mm. Hg.

l 1 Cl CH=CHC2H5 16. c1 Boiling point I to 143 C./0.2

mm. Hg. C1 N CH=C H-C H 17- CH3 Boiling point 139 to 142 C./O.2 mm. Hg. 01- -N= 1 C 11:0 II- 0 Ha 18 Br Boiling point 167 to 171 C./0.3

mm. Hg. Cl -N= H3C--C=CHCHa 19 Boi11ng point 158- Hg. 01- N 1 H3 CHICK-C2115 Boiling point 152- 157/0.3 mm. Hg.

Boillng point 158- 168/0.3 mm. Hg.

Formulae of Examples 2 34 Physical constants Formulae of Examples 2-34 Physical constants 22-.-- OH; j Boiling point 17317s/0.5 Cl- Ni 5 I I mm. Hg.

01 CH=CHC2H5 I l H30 CH=C 23-... C1 Boiling point 162- 2L gg 0.7 mm. 02115 N N/ CH3 l .t .W. O1 I EXAMPLE 35 or-n n 01 I ram-at? C1-@- a N CH3 =Q :C/ CH:

738 g of 2-methy1-4-chloro-aniline hydrochloride g pgint (97.8 percent strength) are introduced into 618 g of L J 31 3 20 N-isobutenyl-pyrrolidone at C. Thereafter, C1T N N CH3 660 g of phosphorus oxychloride are added'dropwise at l 15 20C, with slight cooling. The mixture is then T stirred for a further hour at 20C andis warmed to 80C 26 Cl C1 02115 B 1 in the course of one hour. In the course thereof, a vig- {g i gjg i orous evolution of hydrogen chloride starts. The mix- L Hg ture is stirred for approximately a further hour at 80 N CH3 85C, until 2-methyl-4-chloro-aniline is no longer de- L tectable by diazotisation and coupling. The batch is al- \C2H5 3O lowed to cool somewhat, and the viscous melt is poured. v Boiling point into 30 litres of water at 20 25C, while stirring well. i After one hour, all has dissolved apart from small Cl-N N CH amounts of oil by-products. Active charcoal and filtra- 3 tion aid are added and the acid solution of the reaction 01 product is clarified by filtration. percent strength so 02m dium hydroxide solution is added dropwise to the til- 2s.... 31 Bt i ingnggkng trate at 20 25C, while stirring well and cooling, until J mm. H pH 8.5 is reached. The reaction product precipitates in C1 N N 02m the form of a pale yellowish-coloured crystalline sus- (IJPPC 4O pension; seeding is used if necessary. After completion l of the precipitation, the mixture is stirred for a further I 02115 30 minutes at 20 and the crystalline product is filtered 9- gg gj geleg off and washed with a large amount of water. After dry- 1 12- ing invacuo, the yield is 920 g (86.5 g of theory). Melt- N cam 45 ing point: 68 70C; after recrystallisation from petro- Cl leum ether, melting point: 71 72C. The purity of the 02115 crude product, determined by gas chromatography, 1s Boiling point 98 99.5 percent. I

l I 15.??? EXAMPLE 36 (ll-@N N OzHs I H=C 31.-.- Cl 01 2 5 Boiling point \N I 168-173/0.2 J3E=C mm. Hg. N 111/ CzHi 100 g of 4-chloroaniline and 126 g of N-isobutenyl- CzHr pyrrolidone are dissolved in 800 ml of benzene and 132 32.... CH; ggigf ggb g g of phosphorus oxychloride are added dropwise at 7 mm. Hg. 20C, with stirring. Thereafter the mixture is heated to C1 N @2115 reflux in the course of one hour and is kept refluxing c for 1 2 hours, until 4-chloroaniline is no longer detectable in a sample by diazotisation and coupling. Br Boiling point Thereafter the batch, from which the reactionproduct 171-17s 0.4 has precipitated as a lower oily layer, is pured into 5 li- L mm tres of ice water and 300 m1 of 45 percent strength sof /C2H5 dium hydroxide solution, whilst stirring. The benzene CH=C layer is separated off and dried over potassium carbonate the solvent is distilled off and the reaction product boiling pointlm l58l62C; yield 173 g-(8l percent of theory).

The compounds of Examples 3739 are analogously produced from the appropriate N-substituted pyrrolidones and arylamincs.

The compounds of Examples 4056 are analogously produced from the appropriate N-substituted pyrrolidones-and arylamines.

Ex. N0. Formulae of Examples 40-56 Physical constants 40.-.- C1 C1 Boiling l pointm mmJ 155- 158?. N N CH:

41..-- G1 Boiling pointm mm.I 168- 172. 01 N I T CHa C1 CH=C 42.... OH; Boiling points: 111111.: 167- 1 172. 01- N N CH3 1 O1 CH=C 43-... CH Bolling a polntm mm; 155- 159. Br N- III on; CH=C a a 2. 44.... C1 CH3 Boiling l pO tfl-(lmm-I 158 to 163 N OH:

I CH=C 9 3?. 45.-.. C1 Boiling pointo-s mun-1 156 to 161 C. N

N CH3 (BH=C Ex. No. Formulae of Examples 4-0-56 Physical constants 46.... C1 Boiling pointm mm.1 165 Q to 171 0.

N: l 1? /CH3 Cl C H=C 4-7.- Cl Boiling gollngawmg 153 on N O N 3 JET-C 48.... Cl Boiling I pointm m 153 01 N to 156 C.

N 0 Ha I C1 H=C 49.." CH Boiling DOiI'ItD-Q mm-I 01 N to 147 C.

l CH=CH-CH2-CHI 50. Br Boiling point 172- l 1s0[0.5 mm.

Hg. III CH3 C H=C 51. Br Boiling noint 175 18 /0.15 mm. B r N Hg I |T CH3 CH=C 52- Cl Boiling point 163- a EGVOB mm.

If CH3 I CH=C 53.... Cl Boiling point 165- J I gv/oz mm.

g. Br- N- III CH3 CzHs V 54- Br B oiling point 162- I 168[0.2 mm.

1? 0 Ha CH=C C2H5 V 55.. G1 Boiling polnt- I 1so 0.2 mm. I III CH3 C1 CH=C C2Hs 56- C H; Boilin point 164- l J 169 0.3 mm.

I? CH3 CH==C C2Hs in vitro test of ovicidal action on ticks 3 g of each active substance to be tested are mixed with 7 g of a mixture of equal parts by weight of ethylene glycol monomethyl ether and'nonylphenyl polyglycol ether. The emulsion concentrate thus obtained is diluted with water to the particular desired use concentration.

Adult fully bloated female ticks of the variety Boophilus microplus (resistant) are dipped for one minute into this active substance preparation. After dipping 10 female specimens of each ofthe various tick strains, the individual ticks are transferred into plastic dishes, the base of which is covered with a disc of filter paper.

After days the activity of each active substance preparation is determined by assessing the inhibition of deposition of fertile eggs, as compared to the deposition of eggs by untreated control ticks. The action is indicated in percent: 100 percent means that no further fertile eggs were deposited and percent means that the ticks have laid half the number of eggs laid by the untreated control ticks.

Table A sets forth the results from two representative compounds of Belgian patent No. 734,934, while Table B sets forth the results from representative compounds of the present invention.

TABLE A.-IN VITRO TEST FOR OVICIDAL ACTION ON TICKS Source of active substance- Active substance Ovicidal action against Boophilus, Biarra strain 50% inhibition inhibition the indicated active substance concentration According to Belgian Patent 734,934..-

Example 2.

Example 73.

TABLE B.-IN VITRO TEST FOR OVICIDAL ACTION ON TICKS Ovicidal action against Boophilus, Biarra strain 50% inhibition inhibition at at- Compounds or the The indicated active present substance concentration Invention Active substance Physical constants (percent by Weight) Example 1 ([71 J Melting point: 54.5" 0. Boiling point 0.2 mm; 158 0.003 0.001

Q I I CH CH=C Example 35 3 Melting point: 71-72 C 0. 01 0. 003

N /CH:

JH=O\ swamp. a 7Q EL 7... fun s Example40 or 21 Boiling point M m: 15s-15s 0.01 0. 003

N i Q I cH- CH=O\ Example 41 Cl Boiling point M mm; 168-172 0. 01 0. 003

I /C H3 01 G H=C TABLE B.IN vnno TEST FOR OVICIDAL ACTION ON TICKS -Continued Ovicidal action against Boophilus, Biarra. strain 105% inhibition inhibition at at Compounds of the The indicated active present substance concentration Invention Active substance Physical constants (percent by weight) Example 42 CH3 Boiling point mm; 167172 0.03 0.01 I At a concentration of 0.0003% the compound Cl N has a lethal effect If /C H: 011 tick larvae c1 0 H=C CH Example 43 (3H3 U Boiling point 0.3 mm; -159" 0. 01 0.005

I}! C H; C H=C 9 Example 44." (Ill (3113 4' Boiling point M mm; 158 to 163 C 0. 01 0. 0 05 J Q \N Example 36--. T Boiling point 0.3 mm; 158 to 162 C 0.03 0. 02

Cl- N- C H=G\ Example 45... ('31 Boiling point m 156 to 161 C 0. 03 0. 02

N G \N/ C Example 46... (I31 Boiling point 0.; m 165 to 171 C 0.03 0.01

N Q N 0 Hi I Cl C 11:0

Example 47- I Cl Boiling point 0.3 mm; 153 to 156 C 0.03 0.02

J N C H:

C H=C Example 48. Cl I Boiling point ,3 mm; to 164 C 0.03 0.02

01- Ni Y N 6 Ha I Cl 0 11:0

Example 49... ([JH; Boiling point 11.: m 145 to 147 C. 0.003 0. 00

Cl N J GH=C H-O H2CH;

Emmm 5() 13 Boiling point l72l80/0.5 mm. Hg 0.01 0. 005

I J Cl N- Il I 0HJ CH=C TABLE B.-1N VITRO TEST FOR OVICIDAL ACTION ON TIGKS-Contlnued Ovlcidal action against Boophilus, Blarra strain lnh i lg on lnhll llfibn Compounds of the The indicated active fri e n t ion Active substance Physical constants g e efil t g v glgflll Example 51-.. 13r Boiling point 175180/O.15 mm. Hg 0. 01 0,003

Br N \N/ CH;

AHZO

CH3 Example 52... :1 U I Boiling point 163166/0.3 mm. Hg 0.01 0. s

C1*N=\N/ CH:

Example 53 (31 I Boiling point 165174/0.2 mm. Hg. 0. 03 0.01

Br- N \N/ CH3 CzHs Example 54 1'31 Boiling point 162-168/0.2 mm. Hg 0.03 0. 01

O1 N\N/ CH:

oH=o

CzHs

Example 55-.. G1 I Boiling point 175-180/0.2 mm. Hg 0. 03 0.01

01 N=\NJ CH3 1 (111:0

CzH

Example 56 (IJHa I Boiling point 164169/0.3 mm. Hg 0.01 0.003

What is claimed is: g 2. A compound according to claim 1, wherein R is 1. A compound of th f l chlorine, bromine or fluorine, R is hydrogen, chlorine,

bromine, fluorine, methyl, ethyl, difluoromethyl or tric -cH, fluoromethyl, and R is hydrogen or alkyl of l to 4 cari R; bon atoms. I 3. A compound according to claim 2, wherein N B R is chlorine or bromine, 2 R is hydrogen, chlorine, bromine, methyl, ethyl or C trifluoromethyl,

or a salt thereof,

wherein R;, is hydrogen,

n is l or 2, and

A, B and C each represent hydrogen, methyl or ethyl,

' or A and B,-or B and C are alkyl or alkenyl linked to each other to form a 6-membered ring, provided that, at least one of A, B and C is alkyl or alkenyl.

4. The compound according to claim 1 which is R is halogen,

R is hydrogen, halogen, alkyl of l to 6 carbon atoms, 60

difluoromethyl or trifluoromethyl,

R is hydrogen or lower alkyl,

n is an integer from I to 4, and

A, B and C each represent hydrogen, alkyl of l to 6 l carbon atoms, alkenyl of 2 to 6 carbon atoms, or L A and B, or B and C, are linked to each other to N CH; form a ring, provided that, at least one of A, B and E C is alkyl or alkenyl. CH;

5. The compound according to claim 1 which is 6. The compound according to claim 1 which is 7. The compound according to claim 1 which is NJ I 8. The compound according to claim 1 which is 9. The compound according to claim 1 which is 10. The compound according to claim 1 which is I CH=C 11. The compound according to claim I which is 13. The compound according to claim 1 which is U CH 14. The compound according to claim 1 which is 15. The compound according to claim 1 which is N -Q Q All CH=C 16. The compound according to claim 1 which is 17. The compound according to claim 1 which is c1 7, II=CII-C2H 18. The compound according to claim 1 which is 19. The compound according to claim I which is 20. The compound according to claim 1 which is 21. The compound according to claim 1 which-is 23. The compound according to claim 1 which is Q- lN/ 24. The compound according to claim 1 which is 25. The compound according to claim 1 which is 26. The compound according to claim 1 which is 27. The compound according to claim 1 which is 28. The compound according to claim I which is 29. The compound according to claim 1 which is '-Nl Q N oH=o I 02115 30. The compound according to claim 1 which is Cl- -N=[ N CH3 31 The compound according to'claim l which is I 32. The compound according to claim 1 which is -Q-il I N CzHs 33. The compound according to claim 1 which is 34. The compound according to claim 1 which is 3s. ri gsaggqnaae srdng 0 claimiT which is (III-Ia 01 Nl 36. The compound according to claim 1 which is CzHs 37. The compound according to claim 1 which is Q- iNJ CzHs H34) 41H: C

38. The-compound according to claim 1 which is 39. The compound according to claim 1 which is -Qaj 41. The compound according to claim 1 which is 42. The compound according to claim 1 which is Q ZQ 43. The compound according to claim 1 which is 44. The Compound according to claim 1 which is Cl 01 all J N CH 45. The compound according to claim 1 whichis CH: 01- N= J N CH 46. The compound according to claim 1 which is 47. The compound according to claim 1 which is Cl CH3 I i Q N 48. The compound according to claim 1 which is 49. The compound according to claim 1 which is N CH: 1 H=C 50. The compound accordingtoclaim l which is l N CH:

51. The compound according to claim 1 which is Cl (31- Nl J N CH 52. The compound according to claim 1 which is --53. The compound according to claim 1 which is 54. The compound according to claim 1 which is 55. The compound according to claim 1 which is 56. The compound according to claim 1 which is 57. The compound according to claim 1 which is 58. The compound according to claim 1 which is 59. The compound according to claim 1 which is 

2. A compound according to claim 1, wherein R1 is chlorine, bromine or fluorine, R2 is hydrogen, chlorine, bromine, fluorine, methyl, ethyl, difluoromethyl or trifluoromethyl, and R3 is hydrogen or alkyl of 1 to 4 carbon atoms.
 3. A compound according to claim 2, wherein R1 is chlorine or bromine, R2 is hydrogen, chlorine, bromine, methyl, ethyl or trifluoromethyl, R3 is hydrogen, n IS 1 or 2, and A, B and C each represent hydrogen, methyl or ethyl, or A and B, or B and C are alkyl or alkenyl linked to each other to form a 6-membered ring, provided that, at least one of A, B and C is alkyl or alkenyl.
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